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US12421385B2 - Resin composition - Google Patents

Resin composition

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Publication number
US12421385B2
US12421385B2 US17/763,866 US202017763866A US12421385B2 US 12421385 B2 US12421385 B2 US 12421385B2 US 202017763866 A US202017763866 A US 202017763866A US 12421385 B2 US12421385 B2 US 12421385B2
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United States
Prior art keywords
resin composition
mass
diene
less
anhydride
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US17/763,866
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US20220340748A1 (en
Inventor
Yoji Yamashita
Takuya Yokomichi
Kenji Kashihara
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Toyobo Co Ltd
Toyobo MC Corp
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Toyobo MC Corp
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Assigned to TOYOBO CO., LTD. reassignment TOYOBO CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KASHIHARA, KENJI, YAMASHITA, YOJI, YOKOMICHI, Takuya
Publication of US20220340748A1 publication Critical patent/US20220340748A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the present invention relates to a resin composition, and more specifically to a modified propylene-based resin composition.
  • Polyolefin materials such as polypropylene and polyethylene, are used in various industrial fields because of their easy availability and excellent molding processability. However, since polyolefins do not contain a polar group in their molecules, they are chemically inert, and thus extremely difficult to paint or bond. against such a problem, acid-modified polyolefin resins have been proposed as paint pretreatment agents, adhesives, or compatibilizers.
  • Modification of polyolefin resins by introducing a polar group by graft modification with an unsaturated carboxylic acid such as a maleic anhydride or a derivative thereof has been well known, and widely practiced.
  • an unsaturated carboxylic acid such as a maleic anhydride or a derivative thereof
  • a grafting reaction using a graft initiator such as an organic peroxide
  • the conventional method produces a large amount of reaction residue, which reduces the physical properties of a graft modified product.
  • Patent Literature 1 proposes a method of performing a radical reaction in the presence of added rubber.
  • Patent Literature 2 proposes graft modification in the co-presence of solid rubber and an unsaturated aromatic monomer.
  • An object of the present invention is to provide a modified polyolefin resin composition that contains a large amount of an unsaturated carboxylic acid or an anhydride thereof, and that can inhibit an increase in fluidity after graft modification due to little influence of a reaction residue, and that, wherein the resin composition when used as a compatibilizer for reinforced fiber plastics provides a molded article with excellent mechanical properties such as bending strength and impact resistance.
  • the present inventors conducted extensive research and found a modified polyolefin resin composition that contains a specific diene-based elastomer, has a high content of an unsaturated carboxylic acid or anhydride thereof, and has less change in fluidity after graft modification due to little influence of a reaction residue, and has excellent physical properties and compatibility.
  • the present invention was proposed. Specifically, the present invention includes the following structure.
  • a resin composition comprising a copolymer of a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or anhydride thereof (C), wherein the content of the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition is 2.0 mass % or more, the melt mass flow rate of the resin composition measured at 190° C./2.16 kg as defined in JIS K 7210 is 2 g/10 min or more and 500 g/10 min or less, and a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition is less than 2.0 mass %.
  • the resin composition preferably contains a volatile hydrocarbon compound in an amount of 0.5 mass % or less.
  • the number average molecular weight of the diene-based elastomer (B) is preferably 50,000 or more, and the content of the diene-based elastomer (B) is preferably 5 to 50 parts by mass relative to 100 parts by mass of the propylene-based polymer (A).
  • a compatibilizer comprising the resin composition according to any of the foregoing.
  • a compatibilizer for glass fiber-reinforced plastics comprising the resin composition according to any of the foregoing.
  • a fiber-reinforced plastic comprising the compatibilizer as described above.
  • the resin composition of the present invention has excellent compatibility with reinforcing fibers such as carbon fibers and glass fibers because of a high content of an unsaturated carboxylic acid or anhydride thereof.
  • the resin composition when used as a compatibilizer for glass fiber-reinforced plastics, mechanical properties such as impact resistance and bending strength of a molded article are improved.
  • the resin composition has high processability, and contains a reaction residue and a volatile hydrocarbon compound in a small amount, which reduces odor.
  • propylene-based polymer (A) used in the present invention there is no limitation on the propylene-based polymer (A) used in the present invention; however, a homopolypropylene or propylene- ⁇ -olefin copolymer can be used.
  • the propylene-based polymer (A) preferably contains a propylene component in an amount of 40 mol % or more, more preferably 50 mol % or more, even more preferably 60 mol % or more, and particularly preferably 70 mol % or more.
  • the propylene- ⁇ -olefin copolymer is obtained by copolymerizing an ⁇ -olefin with propylene as a main material.
  • ⁇ -olefin ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, and vinyl acetate can be used singly or in combination.
  • ethylene and 1-butene can be preferably used, and 1-butene can be more preferably used.
  • the melting point of the propylene-based polymer (A) is preferably 70° C. or more and 170° C. or less, more preferably 120° C. or more, and even more preferably 140° C. or more. The higher the melting point, the higher the crystallinity, which increases the mechanical strength of a molded product when the resin composition is mixed with polypropylene as a compatibilizer.
  • the melt mass flow rate of the propylene-based polymer (A) is preferably 1 g/10 min or more and 100 g/10 min or less, more preferably 50 g/10 min or less, and even more preferably 20 g/10 min or less. When the melt mass flow rate is 100 g/10 min or more, granulation in producing the resin composition of the present invention becomes difficult.
  • the diene-based elastomer (B) used in the present invention is a polymer comprising a diene compound as a main component, and has a double bond in the main chain.
  • diene-based elastomer (B) examples include acrylonitrile butadiene-based elastomers, butadiene isoprene copolymers, styrene isoprene copolymers, butadiene pentadiene copolymers, styrene butadiene elastomers, styrene butadiene copolymers, polychloroprene, polyisoprene, and polybutadiene.
  • styrene-butadiene copolymers and polybutadiene can be used.
  • the diene-based elastomer (B) must have a number average molecular weight of 50000 or more, preferably 70000 or more, and more preferably 80000 or more.
  • the resin composition has excellent processability and a molded article obtained by using the resin composition as a compatibilizer for glass fiber-reinforced plastics has excellent mechanical properties such as impact resistance.
  • the upper limit of the number average molecular weight is preferably 300000 or less, and more preferably 200000 or less.
  • the dispersibility with the propylene-based copolymer (A) becomes excellent, and the addition amount of the unsaturated carboxylic acid or anhydride thereof to the resin composition becomes uniform, which increases adhesion to polyolefin resins.
  • the use of the diene-based elastomer having a number average molecular weight as low as less than 50000 is not desirable because of the possibility of poor adhesion to and poor compatibility with olefin resins.
  • the content of the diene component in the diene-based elastomer (B) is preferably 30 mass % or more and 100 mass % or less, more preferably 35 mass % or more, and even more preferably 40 parts by mass or more.
  • a polybutadiene elastomer is most preferred from the viewpoint of attaining high acid addition.
  • the melting point (Tm) of the diene-based elastomer (B) is preferably 50° C. or more and 120° C. or less, more preferably 60° C. or more, and even more preferably 80° C. or more.
  • a diene-based elastomer (B) having a melting point of 120° C. or more causes incompatibility due to poor melting during kneading in an extruder, which may reduce the physical properties of the modified polyolefin resin composition and acid addition.
  • diene-based elastomers (B) can be used alone or in a combination of two or more.
  • the unsaturated carboxylic acid or anhydride thereof (C) used in the present invention is a compound having both a C ⁇ C unsaturated bond in the molecule and a carboxylic acid group or acid anhydride group thereof.
  • the resin composition can provide compatibility with glass fibers because it has a carboxylic acid group or an acid anhydride group thereof. Further, having an unsaturated bond makes the propylene-based polymer (A) and the diene-based elastomer (B) copolymerizable.
  • the unsaturated carboxylic acid or anhydride thereof (C) there is no particular limitation on the unsaturated carboxylic acid or anhydride thereof (C), as long as it has both an unsaturated bond and a carboxylic acid group or anhydride group thereof as described above.
  • examples include acrylic acid, methacrylic acid, nasic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
  • maleic acid is preferred, an acid anhydride is more preferred, and a maleic anhydride is even more preferred.
  • the resin composition of the present invention contains a reaction product obtained by reacting a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or an anhydride thereof (C), wherein the content of the unsaturated carboxylic acid or the anhydride thereof (C) in the resin composition is 2.0 mass % or more of the entire resin composition, and the melt mass flow rate of the resin composition measured at 190° C./2.16 kg as defined in JIS K 7210 is 2 g/10 min or more and 500 g/10 min or less, and the content of the reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition is less than 2.0 mass % of the entire resin composition.
  • the reaction product comprises a copolymer comprising at least a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or anhydride thereof (C), and may further comprise a copolymer of the propylene-based polymer (A) and the unsaturated carboxylic acid or anhydride thereof (C), and/or a copolymer of the diene-based elastomer (B) and the unsaturated carboxylic acid or anhydride thereof (C).
  • the resin composition of the present invention contains 98.0 mass % or more of the reaction product and less than 2.0 mass % of a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C).
  • the resin composition of the present invention must contain the unsaturated carboxylic acid or anhydride thereof (C) in an amount of 2.0 mass % or more, preferably 4.0 mass % or more, and more preferably 5.0 mass % or more.
  • the amount of the unsaturated carboxylic acid or anhydride thereof (C) is preferably 15.0 mass % or less, and more preferably 10.0 mass % or less.
  • the content of the unsaturated carboxylic acid or anhydride thereof (C) is 15.0 mass % or less, high compatibility with polyolefins, in particular, high compatibility with polypropylene can be attained, and mechanical properties when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics are improved.
  • the content of the reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition of the present invention is less than 2.0 mass %, and preferably less than 1.5 mass %. If the content of the reaction residue is 2.0 mass % or more, when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics, mechanical properties such as elongation modulus, bending modulus, and impact resistance is reduced due to the reaction residue. By incorporating the diene-based elastomer, the reaction efficiency of the unsaturated carboxylic acid or anhydride thereof (C) is improved, which can reduce the reaction residue.
  • the resin composition of the present invention has a melt mass flow rate of 2 g/10 min or more and 500 g/10 min or less at 190° C./2.16 kg as defined in JIS K 7210, preferably 300 g/10 min or less, and more preferably 280 g/10 min or less.
  • the melt mass flow rate is preferably 50 g/10 min or more, more preferably 80 g/10 min or more, and even more preferably 105 g/10 min or more.
  • the resin composition of the present invention preferably contains a volatile hydrocarbon compound in an amount of 0.5 mass % or less, preferably 0.3 mass % or less, and more preferably 0.1 mass % or less.
  • a volatile hydrocarbon compound in an amount of 0.5 mass % or less, preferably 0.3 mass % or less, and more preferably 0.1 mass % or less.
  • the resin composition of the present invention preferably contains the diene-based elastomer (B) in an amount of 5 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 20 mass %, relative to the total amount of the propylene-based polymer (A) and the diene-based elastomer (B).
  • the content of the component of the diene-based elastomer (B) is set to 5 mass % or more, mechanical properties such as impact resistance when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics are improved.
  • the resin composition when used as a compatibilizer for glass fiber-reinforced plastics has excellent compatibility with PP (matrix), which increases mechanical properties.
  • the resin composition of the present invention may further comprise glass fibers.
  • the resin composition of the present invention can be used as a compatibilizer, and the compatibilizer containing the resin composition of the present invention is preferably used as a compatibilizer for glass fiber-reinforced plastics.
  • the method for producing the resin composition of the present invention is not particularly limited, and examples include a radical grafting reaction in which a radical species is formed in a polymer serving as a main chain, and an unsaturated carboxylic acid and acid anhydride are graft-polymerized using the radical species as a polymerization starting point.
  • radical generators include, but are not limited to, organic peroxides and azonitriles, with organic peroxides being preferred.
  • organic peroxides include, but are not limited to, di-tert-butylperoxy phthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxy benzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy pivalate, methyl ethyl ketone peroxide, di-cert-butyl peroxide, lauroyl peroxide, and 2,5-dimethyl-2,5-di(tert-butyl propyl)hexane.
  • azonitriles include azobisisobutyronitrile and azobisisopropionitrile.
  • the glass fiber-reinforced plastic containing the compatibilizer of the present invention is used for home appliances and automobile parts.
  • a resin composition (P-1) (2 parts by mass), 58 parts by mass of polypropylene (J-700GP produced by Prime Polymer Co., Ltd.), and 40 parts by mass of glass fiber (ECS03-631K produced by Central Glass Co., Ltd.) were supplied to an extrusion molding machine (LABOTEX30HSS produced by NSK Co., Ltd.) to perform granulation. Thereafter, injection molding was performed using an injection-molding machine (device: TI-30F6 produced by Toyo Machinery & Metal Co., Ltd.) under the conditions of an injection temperature of 190° C. and a molding temperature of 30° C. to form a multi-purpose test piece (Type A1) (Test Specimen 1) as described in JIS K 7139:2009 (ISO 20753).
  • the elongation strength was evaluated using the test pieces prepared above.
  • the evaluation method is based on the method defined in JIS K 7161:2014 (ISO 527-1).
  • Each test piece has a thickness of 3.0 mm, and the elongation strength is evaluated under conditions such that the distance between chucks is 50 mm and the elongation speed is 1.0 ram/min.
  • the measurement temperature is 23° C. unless otherwise specified.
  • the ends of the test pieces produced above were cut using a processing machine (Notching Tool A produced by Toyo Seiki Co., Ltd.) to produce strip test pieces (80 mm ⁇ 10 mm ⁇ 3 mm), and the bending strength was evaluated.
  • the evaluation method is based on the method defined in JIS K 7171:2016 (ISO 178:2010).
  • the bending strength was evaluated under conditions such that the span length was 48 mm and the loading rate was 1.0 mm/min.
  • the measurement temperature is 23° C. unless otherwise specified.
  • test pieces produced above were cut using a processing machine (Notching Tool A produced by Toyo Seiki Co., Ltd.) to produce notched strip test pieces (80 mm ⁇ 10 mm ⁇ 3 mm, notch depth: 2 mm), and the impact resistance test was performed.
  • the evaluation method is based on the Izod impact test method defined in JIS K 7110:1999 (ISO 180).
  • the content of unsaturated carboxylic acid or acid anhydride thereof is the value calculated according to the following equation using the coefficient (f) obtained from the calibration curve prepared using a chloroform solution of maleic anhydride (Tokyo Chemical Industry Co., Ltd.) with FT-IR (FT-IR8200PC produced by Shimadzu Corporation), and the absorbance (I) of elongation peak (1780 cm ⁇ 1 ) of carbonyl (C ⁇ O) bonding of maleic anhydride in a sample, wherein the sample is each of the resin composition samples after acetone washing, which is used as a 10 mass % toluene solution sample.
  • the content of a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition of the present invention was measured according to the following “Low Molecular Weight Content” section.
  • the melt mass flow rate is measured based on the method defined in JIS K6758.
  • the measurement temperature was 190° C., and the measurement was conducted at a load of 2.16 kg unless otherwise specified.
  • the content of a volatile hydrocarbon compound is a value calculated from the remaining weight.
  • Content of volatile hydrocarbon compound [mass %] [(the weight of resin before being allowed to stand ⁇ the weight of resin after being allowed to stand)/the weight of resin before being allowed to stand] ⁇ 100
  • Example 2 The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 4 parts by mass, thus obtaining a resin composition (P-2).
  • the evaluation results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 16 parts by mass, thus obtaining a resin composition (P-3).
  • the evaluation results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was performed except that the amount of the di-tert-butyl peroxide used in Example 1 was changed to 1 part by mass, thus obtaining a resin composition (P-4).
  • the evaluation results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was performed except that the amount of the di-tert-butyl peroxide used in Example 1 was changed to 4 parts by mass, thus obtaining a resin composition (P-5).
  • the evaluation results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was performed except that the supply amount of the diene-based elastomer (B-1) used in Example 1 was changed to 5 parts by mass, thus obtaining a resin composition (P-6).
  • the evaluation results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was performed except that the supply amount of the diene-based elastomer (B-1) used in Example 1 was changed to 50 parts by mass, thus obtaining a resin composition (P-7).
  • the evaluation results are shown in Table 1.
  • Example 2 The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 2 parts by mass, thus obtaining a resin composition (P-8).
  • Example 2 The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 20 parts by mass, thus obtaining a resin composition (P-9).
  • Example 2 The same procedure as in Example 1 was performed except that the amount of the di-tert-butyl peroxide used in Example 1 was changed to 6 parts by mass, thus obtaining a resin composition (P-10).
  • Example 1 The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 20 parts by mass and the reaction temperature was changed to 140° C., thus obtaining a resin composition (P-11).
  • Example 2 The same procedure as in Example 1 was performed except that the diene-based elastomer was changed from (B-1) to (B-2), thus obtaining a resin composition (P-12).
  • Example 2 The same procedure as in Example 1 was performed except that the diene-based elastomer was changed to 0 parts by mass, thus obtaining a resin composition (P-13).
  • Example 2 The same procedure as in Example 1 was performed except that the diene-based elastomer was changed to 70 parts by mass, thus obtaining a resin composition (P-14).
  • the propylene-based polymer (A) used in each of the Examples and Comparative Examples is as follows.
  • the diene-based elastomer (B) used in each of the Examples and Comparative Examples is as follows.
  • the resin composition of the present invention contains a small amount of a reaction residue of a carboxylic acid compound while having a certain amount of acid addition, and contains a copolymer of a propylene-based polymer, a high-molecular-weight diene-based elastomer, and an unsaturated carboxylic acid or anhydride thereof, the resin composition of the present invention has excellent interfacial adhesion with glass. Accordingly, the resin composition of the present invention can be used as a compatibilizer for glass fiber-reinforced plastics.

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Abstract

This invention provides a modified polyolefin resin composition that contains a large amount of an unsaturated carboxylic acid or an anhydride thereof, and that can inhibit an increase in fluidity after graft modification due to little influence of a reaction residue, wherein the resin composition when used as a compatibilizer for reinforced fiber plastics provides a molded article with excellent mechanical properties such as bending strength and impact resistance.

Description

TECHNICAL FIELD
The present invention relates to a resin composition, and more specifically to a modified propylene-based resin composition.
BACKGROUND ART
Polyolefin materials, such as polypropylene and polyethylene, are used in various industrial fields because of their easy availability and excellent molding processability. However, since polyolefins do not contain a polar group in their molecules, they are chemically inert, and thus extremely difficult to paint or bond. Against such a problem, acid-modified polyolefin resins have been proposed as paint pretreatment agents, adhesives, or compatibilizers.
Modification of polyolefin resins by introducing a polar group by graft modification with an unsaturated carboxylic acid such as a maleic anhydride or a derivative thereof has been well known, and widely practiced. As a method of grafting an unsaturated carboxylic acid derivative and anhydride thereof onto a polyolefin, a grafting reaction using a graft initiator such as an organic peroxide is known. However, due to the low grafting efficiency of the unsaturated carboxylic acid or derivative thereof, the conventional method produces a large amount of reaction residue, which reduces the physical properties of a graft modified product.
Accordingly, Patent Literature 1 proposes a method of performing a radical reaction in the presence of added rubber. Patent Literature 2 proposes graft modification in the co-presence of solid rubber and an unsaturated aromatic monomer.
CITATION LIST Patent Literature
  • PTL 1: JP1980-50040A
  • PTL 2: Japanese Patent No. 2632980
SUMMARY OF INVENTION Technical Problem
However, although in the method described in Patent Literature 1, the amount (addition amount) of unsaturated carboxylic acid grafted is improved, separate addition of a graft monomer and a radical generator requires a long reaction time, leading to a problem in terms of economic efficiency and profitability. Moreover, an unreacted residue of rubber having a low molecular weight is present, and the fluidity (melt flow rate) significantly increases between before and after graft modification, resulting in a problem of reduced physical properties, such as poor adhesion to or poor compatibility with olefin resins. In the method described in Patent Literature 2, the amount of unsaturated carboxylic acid grafted did not even reach 1.0 mass %, leading to a problem of poor compatibility with glass fibers.
An object of the present invention is to provide a modified polyolefin resin composition that contains a large amount of an unsaturated carboxylic acid or an anhydride thereof, and that can inhibit an increase in fluidity after graft modification due to little influence of a reaction residue, and that, wherein the resin composition when used as a compatibilizer for reinforced fiber plastics provides a molded article with excellent mechanical properties such as bending strength and impact resistance.
Solution to Problem
To solve the above problems, the present inventors conducted extensive research and found a modified polyolefin resin composition that contains a specific diene-based elastomer, has a high content of an unsaturated carboxylic acid or anhydride thereof, and has less change in fluidity after graft modification due to little influence of a reaction residue, and has excellent physical properties and compatibility. Thus, the present invention was proposed. Specifically, the present invention includes the following structure.
A resin composition comprising a copolymer of a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or anhydride thereof (C), wherein the content of the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition is 2.0 mass % or more, the melt mass flow rate of the resin composition measured at 190° C./2.16 kg as defined in JIS K 7210 is 2 g/10 min or more and 500 g/10 min or less, and a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition is less than 2.0 mass %.
The resin composition preferably contains a volatile hydrocarbon compound in an amount of 0.5 mass % or less.
The number average molecular weight of the diene-based elastomer (B) is preferably 50,000 or more, and the content of the diene-based elastomer (B) is preferably 5 to 50 parts by mass relative to 100 parts by mass of the propylene-based polymer (A).
The resin composition according to any of the foregoing, further comprising a glass fiber.
A compatibilizer comprising the resin composition according to any of the foregoing.
A compatibilizer for glass fiber-reinforced plastics comprising the resin composition according to any of the foregoing.
A fiber-reinforced plastic comprising the compatibilizer as described above.
Advantageous Effects of Invention
The resin composition of the present invention has excellent compatibility with reinforcing fibers such as carbon fibers and glass fibers because of a high content of an unsaturated carboxylic acid or anhydride thereof. For example, when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics, mechanical properties such as impact resistance and bending strength of a molded article are improved. Further, the resin composition has high processability, and contains a reaction residue and a volatile hydrocarbon compound in a small amount, which reduces odor.
DESCRIPTION OF EMBODIMENTS
The embodiments of the present invention are detailed below.
Propylene-Based Polymer (A)
There is no limitation on the propylene-based polymer (A) used in the present invention; however, a homopolypropylene or propylene-α-olefin copolymer can be used.
The propylene-based polymer (A) preferably contains a propylene component in an amount of 40 mol % or more, more preferably 50 mol % or more, even more preferably 60 mol % or more, and particularly preferably 70 mol % or more. The higher the propylene content, the better the compatibility with the polypropylene resin when the propylene-based polymer is used as a compatibilizer.
The propylene-α-olefin copolymer is obtained by copolymerizing an α-olefin with propylene as a main material. As the α-olefin, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, and vinyl acetate can be used singly or in combination. Of these α-olefins, ethylene and 1-butene can be preferably used, and 1-butene can be more preferably used.
The melting point of the propylene-based polymer (A) is preferably 70° C. or more and 170° C. or less, more preferably 120° C. or more, and even more preferably 140° C. or more. The higher the melting point, the higher the crystallinity, which increases the mechanical strength of a molded product when the resin composition is mixed with polypropylene as a compatibilizer.
The melt mass flow rate of the propylene-based polymer (A) is preferably 1 g/10 min or more and 100 g/10 min or less, more preferably 50 g/10 min or less, and even more preferably 20 g/10 min or less. When the melt mass flow rate is 100 g/10 min or more, granulation in producing the resin composition of the present invention becomes difficult.
Diene-Based Elastomer (B)
There is no limitation on the diene-based elastomer (B) used in the present invention; however, the diene-based elastomer (B) is a polymer comprising a diene compound as a main component, and has a double bond in the main chain. Examples of the diene-based elastomer (B) include acrylonitrile butadiene-based elastomers, butadiene isoprene copolymers, styrene isoprene copolymers, butadiene pentadiene copolymers, styrene butadiene elastomers, styrene butadiene copolymers, polychloroprene, polyisoprene, and polybutadiene. Preferably, styrene-butadiene copolymers and polybutadiene can be used.
The diene-based elastomer (B) must have a number average molecular weight of 50000 or more, preferably 70000 or more, and more preferably 80000 or more. By setting the number average molecular weight of the diene-based elastomer (B) to 50000 or more, the resin composition has excellent processability and a molded article obtained by using the resin composition as a compatibilizer for glass fiber-reinforced plastics has excellent mechanical properties such as impact resistance. The upper limit of the number average molecular weight is preferably 300000 or less, and more preferably 200000 or less. When the value is equal to or less than the above value, the dispersibility with the propylene-based copolymer (A) becomes excellent, and the addition amount of the unsaturated carboxylic acid or anhydride thereof to the resin composition becomes uniform, which increases adhesion to polyolefin resins. The use of the diene-based elastomer having a number average molecular weight as low as less than 50000 is not desirable because of the possibility of poor adhesion to and poor compatibility with olefin resins.
The content of the diene component in the diene-based elastomer (B) is preferably 30 mass % or more and 100 mass % or less, more preferably 35 mass % or more, and even more preferably 40 parts by mass or more. In particular, a polybutadiene elastomer is most preferred from the viewpoint of attaining high acid addition.
The melting point (Tm) of the diene-based elastomer (B) is preferably 50° C. or more and 120° C. or less, more preferably 60° C. or more, and even more preferably 80° C. or more. A diene-based elastomer (B) having a melting point of 120° C. or more causes incompatibility due to poor melting during kneading in an extruder, which may reduce the physical properties of the modified polyolefin resin composition and acid addition.
These diene-based elastomers (B) can be used alone or in a combination of two or more.
Unsaturated Carboxylic Acid or Anhydride Thereof (C)
The unsaturated carboxylic acid or anhydride thereof (C) used in the present invention is a compound having both a C═C unsaturated bond in the molecule and a carboxylic acid group or acid anhydride group thereof. The resin composition can provide compatibility with glass fibers because it has a carboxylic acid group or an acid anhydride group thereof. Further, having an unsaturated bond makes the propylene-based polymer (A) and the diene-based elastomer (B) copolymerizable.
There is no particular limitation on the unsaturated carboxylic acid or anhydride thereof (C), as long as it has both an unsaturated bond and a carboxylic acid group or anhydride group thereof as described above. Examples include acrylic acid, methacrylic acid, nasic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof. Of these, maleic acid is preferred, an acid anhydride is more preferred, and a maleic anhydride is even more preferred.
Resin Composition
The resin composition of the present invention contains a reaction product obtained by reacting a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or an anhydride thereof (C), wherein the content of the unsaturated carboxylic acid or the anhydride thereof (C) in the resin composition is 2.0 mass % or more of the entire resin composition, and the melt mass flow rate of the resin composition measured at 190° C./2.16 kg as defined in JIS K 7210 is 2 g/10 min or more and 500 g/10 min or less, and the content of the reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition is less than 2.0 mass % of the entire resin composition.
The reaction product comprises a copolymer comprising at least a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or anhydride thereof (C), and may further comprise a copolymer of the propylene-based polymer (A) and the unsaturated carboxylic acid or anhydride thereof (C), and/or a copolymer of the diene-based elastomer (B) and the unsaturated carboxylic acid or anhydride thereof (C). The resin composition of the present invention contains 98.0 mass % or more of the reaction product and less than 2.0 mass % of a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C).
The resin composition of the present invention must contain the unsaturated carboxylic acid or anhydride thereof (C) in an amount of 2.0 mass % or more, preferably 4.0 mass % or more, and more preferably 5.0 mass % or more. By setting the amount of the unsaturated carboxylic acid or anhydride thereof (C) to the above value or more, the compatibility with glass fibers can be improved; moreover, physical properties such as elongation modulus, bending modulus, and impact resistance obtained when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics can be improved. The content of the unsaturated carboxylic acid or anhydride thereof (C) is preferably 15.0 mass % or less, and more preferably 10.0 mass % or less. When the content of the unsaturated carboxylic acid or anhydride thereof (C) is 15.0 mass % or less, high compatibility with polyolefins, in particular, high compatibility with polypropylene can be attained, and mechanical properties when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics are improved.
The content of the reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition of the present invention is less than 2.0 mass %, and preferably less than 1.5 mass %. If the content of the reaction residue is 2.0 mass % or more, when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics, mechanical properties such as elongation modulus, bending modulus, and impact resistance is reduced due to the reaction residue. By incorporating the diene-based elastomer, the reaction efficiency of the unsaturated carboxylic acid or anhydride thereof (C) is improved, which can reduce the reaction residue.
The resin composition of the present invention has a melt mass flow rate of 2 g/10 min or more and 500 g/10 min or less at 190° C./2.16 kg as defined in JIS K 7210, preferably 300 g/10 min or less, and more preferably 280 g/10 min or less. The melt mass flow rate is preferably 50 g/10 min or more, more preferably 80 g/10 min or more, and even more preferably 105 g/10 min or more. By setting the melt mass flow rate to 500 g/10 min or less, when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics, the adhesion strength between the matrix and glass interface is increased, which increases mechanical properties such as adhesion strength, bending strength, and impact resistance. Setting the melt mass flow rate to the above value or less facilitates granulation, and is thus preferred.
The resin composition of the present invention preferably contains a volatile hydrocarbon compound in an amount of 0.5 mass % or less, preferably 0.3 mass % or less, and more preferably 0.1 mass % or less. By setting the content of the volatile hydrocarbon compound in the resin composition to 0.5 mass % or less, when the resin composition is, for example, used as a compatibilizer for glass fiber-reinforced plastics, reduction in mechanical properties due to the volatile hydrocarbon compound can be inhibited. If the content of the volatile hydrocarbon compound is 1.0 mass % or more, not only mechanical properties when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics but also heat resistance will be reduced.
The resin composition of the present invention preferably contains the diene-based elastomer (B) in an amount of 5 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 20 mass %, relative to the total amount of the propylene-based polymer (A) and the diene-based elastomer (B). By setting the content of the component of the diene-based elastomer (B) to 5 mass % or more, mechanical properties such as impact resistance when the resin composition is used as a compatibilizer for glass fiber-reinforced plastics are improved. When the content of the component of the diene-based elastomer (B) is 50 mass % or less, the resin composition when used as a compatibilizer for glass fiber-reinforced plastics has excellent compatibility with PP (matrix), which increases mechanical properties.
In addition to the copolymer of the propylene-based polymer (A), the diene-based elastomer (B), and the unsaturated carboxylic acid or anhydride thereof (C), the resin composition of the present invention may further comprise glass fibers. The resin composition of the present invention can be used as a compatibilizer, and the compatibilizer containing the resin composition of the present invention is preferably used as a compatibilizer for glass fiber-reinforced plastics.
Production Method of Resin Composition
The method for producing the resin composition of the present invention is not particularly limited, and examples include a radical grafting reaction in which a radical species is formed in a polymer serving as a main chain, and an unsaturated carboxylic acid and acid anhydride are graft-polymerized using the radical species as a polymerization starting point.
Examples of radical generators include, but are not limited to, organic peroxides and azonitriles, with organic peroxides being preferred. Examples of organic peroxides include, but are not limited to, di-tert-butylperoxy phthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxy benzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy pivalate, methyl ethyl ketone peroxide, di-cert-butyl peroxide, lauroyl peroxide, and 2,5-dimethyl-2,5-di(tert-butyl propyl)hexane. Examples of azonitriles include azobisisobutyronitrile and azobisisopropionitrile.
Compatibilizer
The resin composition of the present invention can be used as a compatibilizer. The compatibilizer of the present invention can be used for polyolefin resins such as polypropylene and polyethylene; polyethylene terephthalate; nylon; polycarbonate; and matrix resins such as epoxy resins and phenolic resins. Of these, polyolefin resins can be suitably used, and polypropylene resins can be more preferably used. Usable examples of filler species include, glass fibers, carbon fibers, fiber-reinforced plastics, talc, wood powder, and the like. Of these, glass fibers and plastic fibers are preferred, and glass fibers are particularly preferred.
The glass fiber-reinforced plastic containing the compatibilizer of the present invention preferably contains 40 to 95 mass % of the matrix resin, 5 to 60 mass % of the glass fiber, and 1 to 10 mass % of the compatibilizer of the present invention, relative to the total amount of the matrix resin, the glass fiber, and the compatibilizer of the present invention. By setting the each content within the above range, the resin composition exhibits high compatibility with the polyolefin resin and the glass fiber, ensuring excellent kneadability of the resin composition, the polyolefin resin, and the glass fiber.
The glass fiber-reinforced plastic containing the compatibilizer of the present invention is used for home appliances and automobile parts.
EXAMPLES
The present invention is further described in more detail with reference to the examples below. However, the present invention is not limited to the examples.
Preparation of Test Piece
A resin composition (P-1) (2 parts by mass), 58 parts by mass of polypropylene (J-700GP produced by Prime Polymer Co., Ltd.), and 40 parts by mass of glass fiber (ECS03-631K produced by Central Glass Co., Ltd.) were supplied to an extrusion molding machine (LABOTEX30HSS produced by NSK Co., Ltd.) to perform granulation. Thereafter, injection molding was performed using an injection-molding machine (device: TI-30F6 produced by Toyo Machinery & Metal Co., Ltd.) under the conditions of an injection temperature of 190° C. and a molding temperature of 30° C. to form a multi-purpose test piece (Type A1) (Test Specimen 1) as described in JIS K 7139:2009 (ISO 20753).
For each of the resin compositions of Examples 2 to 7 and Comparative Examples 1 to 7, corresponding test pieces were also prepared and tested.
Evaluation of Elongation Strength
The elongation strength was evaluated using the test pieces prepared above. The evaluation method is based on the method defined in JIS K 7161:2014 (ISO 527-1). Each test piece has a thickness of 3.0 mm, and the elongation strength is evaluated under conditions such that the distance between chucks is 50 mm and the elongation speed is 1.0 ram/min. The measurement temperature is 23° C. unless otherwise specified.
Evaluation Criteria
    • A: Significantly excellent (70 MPa or more)
    • B: Excellent (60 MPa or more and less than 70 MPa)
    • C: Practicable (50 MPa or more and less than 60 MPa)
    • D: Impractical (less than 50 MPa)
      Evaluation of Bending Strength
The ends of the test pieces produced above were cut using a processing machine (Notching Tool A produced by Toyo Seiki Co., Ltd.) to produce strip test pieces (80 mm×10 mm×3 mm), and the bending strength was evaluated. The evaluation method is based on the method defined in JIS K 7171:2016 (ISO 178:2010). The bending strength was evaluated under conditions such that the span length was 48 mm and the loading rate was 1.0 mm/min. The measurement temperature is 23° C. unless otherwise specified.
Evaluation Criteria
    • A: Significantly excellent (100 MPa or more)
    • B: Excellent (90 MPa or more and less than 100 MPa)
    • C: Practicable (80 MPa or more and less than 90 MPa)
    • D: Impractical (less than 80 MPa)
      Evaluation of impact Resistance
The ends of the test pieces produced above were cut using a processing machine (Notching Tool A produced by Toyo Seiki Co., Ltd.) to produce notched strip test pieces (80 mm×10 mm×3 mm, notch depth: 2 mm), and the impact resistance test was performed. The evaluation method is based on the Izod impact test method defined in JIS K 7110:1999 (ISO 180).
Evaluation Criteria
    • A: Significantly excellent (7 kJ/m or more)
    • B: Excellent (6 kJ/m or more and less than 7 kJ/m)
    • C: Practicable (5 kJ/m or more and less than 6 kJ/m)
    • D: Impractical (less than 5 kJ/m)
      Content of Unsaturated Carboxylic Acid or Acid Anhydride Thereof
The content of unsaturated carboxylic acid or acid anhydride thereof is the value calculated according to the following equation using the coefficient (f) obtained from the calibration curve prepared using a chloroform solution of maleic anhydride (Tokyo Chemical Industry Co., Ltd.) with FT-IR (FT-IR8200PC produced by Shimadzu Corporation), and the absorbance (I) of elongation peak (1780 cm−1) of carbonyl (C═O) bonding of maleic anhydride in a sample, wherein the sample is each of the resin composition samples after acetone washing, which is used as a 10 mass % toluene solution sample.
Content of unsaturated carboxylic acid or acid anhydride thereof [mass %]=[absorbance (I)×coefficient (f)×100/sample concentration (%)]
The content of a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) in the resin composition of the present invention was measured according to the following “Low Molecular Weight Content” section.
Low Molecular Weight Content
Each of the resin composition samples was fully washed with acetone at 90° C. for 2h to extract a reaction residue. The acetone extract was transferred into a flask and concentrated to dryness at 100° C. in vacuum. The weight of a dry component was calculated by subtracting the weight of the flask before the acetone extract was transferred from the flask containing the extract that was concentrated to dryness. The low molecular weight content of the present invention is a value calculated according to the following formula.
Low molecular weight content [mass %]=[weight of dry component/weight of resin before acetone washing]×100
Melt Mass Flow Rate
The melt mass flow rate is measured based on the method defined in JIS K6758. The measurement temperature was 190° C., and the measurement was conducted at a load of 2.16 kg unless otherwise specified.
Number Average Molecular Weight (Mn)
The number average molecular weight was measured by GPC using THF as an eluent and an Alliance e2695 gel permeation chromatograph produced by Nihon Waters Corporation (hereafter referred to as GPC, standard material: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-806+KF-803, column temperature: 40° C., flow rate: 1.0 ml/min, detector: Photodiode array detector (wavelength: 254 nm=UV ray)).
Content of Volatile Hydrocarbon Compound
Each of the resin composition samples was allowed to stand at 210° C. for 1 hour. The content of a volatile hydrocarbon compound is a value calculated from the remaining weight. Content of volatile hydrocarbon compound [mass %]=[(the weight of resin before being allowed to stand−the weight of resin after being allowed to stand)/the weight of resin before being allowed to stand]×100
Example 1
One hundred parts by mass of polypropylene (A-1), 15 parts by mass of diene-based elastomer (B-1), 8 parts by mass of maleic anhydride, and 2 parts by mass of di-tert-butyl peroxide were added to a twin-screw extruder (TEM-26SX) equipped with a supply part, a compression part, and a measuring part, produced by Toshiba Machine. The reaction was performed at 160° C. After the unreacted maleic anhydride and the reaction decomposition product of di-tert-butyl peroxide in a degassing part were removed, a resin composition (P-1) was obtained. The property values and the property evaluation results of P-1 are shown in Table 1.
Example 2
The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 4 parts by mass, thus obtaining a resin composition (P-2). The evaluation results are shown in Table 1.
Example 3
The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 16 parts by mass, thus obtaining a resin composition (P-3). The evaluation results are shown in Table 1.
Example 4
The same procedure as in Example 1 was performed except that the amount of the di-tert-butyl peroxide used in Example 1 was changed to 1 part by mass, thus obtaining a resin composition (P-4). The evaluation results are shown in Table 1.
Example 5
The same procedure as in Example 1 was performed except that the amount of the di-tert-butyl peroxide used in Example 1 was changed to 4 parts by mass, thus obtaining a resin composition (P-5). The evaluation results are shown in Table 1.
Example 6
The same procedure as in Example 1 was performed except that the supply amount of the diene-based elastomer (B-1) used in Example 1 was changed to 5 parts by mass, thus obtaining a resin composition (P-6). The evaluation results are shown in Table 1.
Example 7
The same procedure as in Example 1 was performed except that the supply amount of the diene-based elastomer (B-1) used in Example 1 was changed to 50 parts by mass, thus obtaining a resin composition (P-7). The evaluation results are shown in Table 1.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Resin composition P-1 P-2 P-3 P-4 P-5 P-6 P-7
Propylene-based polymer (A) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1)
(A) Parts by mass 100 100 100 100 100 100 100
Diene-based elastomer (B) (B-1) (B-1) (B-1) (B-1) (B-1) (B-1) (B-1)
(B) Parts by mass 15 15 15 15 15 5 50
(C) Parts by mass 8 4 16 8 8 8 8
Peroxide 2 2 2 1 4 2 2
Acid component (wt %) 6.9 3 8.3 6.9 6.5 6.8 6.8
Low molecular weight (wt %) 1 0.9 1.9 0.8 1.3 1 1.1
MFR (g/10 min) 249 230 303 50 491 291 35
Volatile hydrocarbon compound (wt %) 0.3 0.2 0.3 0.3 0.3 0.4 0.5
Elongation strength A B B B B B C
Bending strength A B B B B B C
Impact resistance A B B B C C B
For Comparative Examples 1 to 7, resin compositions (P-8) to (P-14) were individually obtained. The evaluation results are shown in Table 2.
Comparative Example 1
The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 2 parts by mass, thus obtaining a resin composition (P-8).
Comparative Example 2
The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 20 parts by mass, thus obtaining a resin composition (P-9).
Comparative Example 3
The same procedure as in Example 1 was performed except that the amount of the di-tert-butyl peroxide used in Example 1 was changed to 6 parts by mass, thus obtaining a resin composition (P-10).
Comparative Example 4
The same procedure as in Example 1 was performed except that the amount of the maleic anhydride used in Example 1 was changed to 20 parts by mass and the reaction temperature was changed to 140° C., thus obtaining a resin composition (P-11).
Comparative Example 5
The same procedure as in Example 1 was performed except that the diene-based elastomer was changed from (B-1) to (B-2), thus obtaining a resin composition (P-12).
Comparative Example 6
The same procedure as in Example 1 was performed except that the diene-based elastomer was changed to 0 parts by mass, thus obtaining a resin composition (P-13).
Comparative Example 7
The same procedure as in Example 1 was performed except that the diene-based elastomer was changed to 70 parts by mass, thus obtaining a resin composition (P-14).
TABLE 2
Comparative Comparative Comparative Comparative Comparative Comparative Comparative
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Resin composition P-8 P-9 P-10 P-11 P-12 P-13 P-14
Propylene-based polymer (A) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1)
(A) Parts by mass 100 100 100 100 100 100 100
Diene-based elastomer (B) (B-1) (B-1) (B-1) (B-1) (B-2) (B-1) (B-1)
(B) Parts by mass 15 15 15 15 15 0 70
(C) Parts by mass 2 20 8 20 8 8 8
Peroxide 2 2 6 2 2 2 2
Acid component (wt %) 1.1 8.5 6.4 5.2 5.7 2.1 7.8
Low molecular weight component (wt %) 0.7 3.3 0.9 3.5 1.8 1.4 1.0
MFR (g/10 min) 155 245 714 243 555 332 1.7
Volatile hydrocarbon compound (wt %) 0.5 0.2 0.3 1.5 0.4 0.3 0.5
Elongation strength D B B C D B D
Bending strength D D D D D B D
Impact resistance D D D D B D C
The propylene-based polymer (A) used in each of the Examples and Comparative Examples is as follows.
    • A-1: Polypropylene (pellet, melt mass flow rate: 9 g/10 min (230° C.))
The diene-based elastomer (B) used in each of the Examples and Comparative Examples is as follows.
    • B-1: Polybutadiene (pellet, density 0.91 g/cm3, Mn=160,000)
    • B-2: Liquid polybutadiene (Mn=8,000, viscosity: 15,000 cps)
INDUSTRIAL APPLICABILITY
Since the resin composition of the present invention contains a small amount of a reaction residue of a carboxylic acid compound while having a certain amount of acid addition, and contains a copolymer of a propylene-based polymer, a high-molecular-weight diene-based elastomer, and an unsaturated carboxylic acid or anhydride thereof, the resin composition of the present invention has excellent interfacial adhesion with glass. Accordingly, the resin composition of the present invention can be used as a compatibilizer for glass fiber-reinforced plastics.

Claims (8)

The invention claimed is:
1. A resin composition comprising a reaction product obtained by reacting a propylene-based polymer (A), a diene-based elastomer (B), and an unsaturated carboxylic acid or anhydride thereof (C),
wherein
the content of the unsaturated carboxylic acid or anhydride thereof (C) is 2.0 mass % or more of the entire resin composition,
the melt mass flow rate of the resin composition measured at 190° C./2.16 kg as defined in JIS K 7210 is 2 g/10 min or more and 500 g/10 min or less,
the content of a reaction residue derived from the unsaturated carboxylic acid or anhydride thereof (C) is less than 2.0 mass % of the entire resin composition,
the content of a volatile hydrocarbon compound in the resin composition is 0.5 mass % or less of the entire resin composition, and
the content of the diene-based elastomer (B) is more than 10 mass % and 50 mass % or less relative to the total amount of the propylene-based polymer (A) and the diene-based elastomer (B).
2. The resin composition according to claim 1, wherein the diene-based elastomer (B) has a number average molecular weight of 50,000 or more.
3. The resin composition according to claim 1, further comprising a glass fiber.
4. The resin composition according to claim 2, further comprising a glass fiber.
5. A compatibilizer comprising the resin composition according to claim 1.
6. A compatibilizer for glass fiber-reinforced plastics, comprising the resin composition according to claim 1.
7. A fiber-reinforced plastic comprising the compatibilizer according to claim 5.
8. The resin composition according to claim 1, wherein the content of a diene component in the diene-based elastomer (B) is 30 wt % or more and 100 wt % or less.
US17/763,866 2019-09-27 2020-09-08 Resin composition Active 2042-08-13 US12421385B2 (en)

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US20220340748A1 (en) 2022-10-27
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